Selective hydrogenation catalyst of α,β-unsaturated ketone using electronically weakly coupled 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(PiPr3)2 moieties

Abstract

A 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2 moieties, its synthesis, and its use as a catalyst.

We claim: 
     
       1. A 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties having the formula I: 
       
         
           
           
               
               
           
         
       
     
     
       2. The 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 1 , wherein the complex is a yellow solid. 
     
     
       3. The 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 1 , wherein the complex is a catalyst. 
     
     
       4. A method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 1 , the method comprising:
 combining 2-mercaptoquinoline, K 2 CO 3 , CH 2 Cl 2 , and Me 0 H to obtain a first reaction mixture; 
 stirring the first reaction mixture for at least about 15 minutes; 
 adding the first reaction mixture to a solution of [{Ru(CO)Cl(P i Pr 3 ) 2 } 2 (μ—{CH═CH—C 6 H 2 —( i Pr) 2 -2,6} 2 —N═N-4,4′)] in CH 2 Cl 2  to obtain a second reaction mixture; 
 stirring the second reaction mixture to obtain a deep yellow solution; 
 removing the CH 2 Cl 2  and MeOH from the second reaction mixture to obtain a yellow precipitate; 
 washing the yellow precipitate to obtain a residue; 
 drying the residue; and 
 obtaining the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties. 
 
     
     
       5. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(PiPr 3 ) 2  moieties of  claim 4 , wherein the 2-mercaptoquinoline and K 2 CO 3  are added in an about 1:1 molar ratio. 
     
     
       6. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 4 , wherein the second reaction mixture is stirred for at least about one hour. 
     
     
       7. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 4 , wherein the yellow precipitate is washed with n-hexane and MeOH. 
     
     
       8. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 4 , wherein the yellow precipitate is washed twice. 
     
     
       9. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 4 , wherein the yellow precipitate is dried in vacuo. 
     
     
       10. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 4 , wherein the [{Ru(CO)Cl(P i Pr 3 ) 2 } 2 (μ—{CH═CHC 6 H 2 —( i Pr) 2 -2,6} 2 —N═N-4,4′)], 2-mercaptoquinoline, and K 2 CO 3  are added in an about 0.5:1.1:1.1 molar ratio. 
     
     
       11. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties of  claim 4 , wherein the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  moieties is obtained as a yellow solid. 
     
     
       12. The method of making the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  of  claim 4 , wherein the 4,4′-divinylazoarylene-bridged diruthenium complex bearing two Ru(CO)(2-mercaptoquinolato)(P i Pr 3 ) 2  compound is obtained in an about 94% yield.